Combining Methods CAN/CGSB-3.0 andASTM D-5580 in a Single GC PlatformZhuangzhi ‘Max’ Wang, PhD, Richard Whitney, PhD, Clif...
IntroductionTo improve productivity and lower the capital cost, a single gas chromatograph hasbeen configured to perform t...
InstrumentationGC-2010Plus Columns:    20% TCEP, 0.558m X     0.75mm                            PONA    Rtx-1 30m X 0.5...
Canadian PONA Method CAN/CGSB-3.0 Objective  Separation of hydrocarbons into types    Paraffins, Olefins, Naphthene,    ...
Canadian PONA Experimental Column: Rtx-1 PONA 100mX0.25mmX0.5µm Sample: Premium Gas Carrier Gas: He, Linear velocity: 2...
Chromatogram   uV(x10,000)5.0 Chromatogram4.54.03.53.02.52.01.51.00.50.0-0.5           5.0     10.0   15.0   20.0   25.0  ...
Manual Chromatogram Quantification     All components are identified and classified
Canadian PONA Report                                                                                              Hydrocar...
ASTM D5580-02Scope:Determination of benzene, toluene, ethylbenzene,xylenes, C9 and heavier aromatics, and totalaromaticsSa...
Two Step AnalysisNo.1Determination of benzene and toluene, with 2-Hexanone as internal standard; backflush C8+aromatics an...
ASTM D-5580 Experimental   INJ Temp: 200 °C, Carrier Gas: He, Flow Control Mode:    Pressure, INJ Pressure: 160KPa, TCEP ...
TCD Chromatogram   uV(x10,000)    Chromatogram1.21.1                         Benzene1.00.9                                ...
Analysis No.1    uV(x1,000,000)                                                                            2-Hexanone     ...
Calibration Curves: Benzene & Toluene
Premium Gas Analysis No.1      uV(x10,000,000)                                                                            ...
Analysis No.2   uV(x1,000,000)    Chromatogram                                                                            ...
Calibration Curves Ethylbenzene, o-Xylene, and1,2,4-Trimethylbenzene
Premium Gas Analysis No.2      uV(x1,000,000)       Chromatogram6.05.5                             %RSD < 1.8%5.0         ...
Conclusions Mechanical valve-based multidimensional GC-2010 Plus has  successfully achieved ASTM D5580 requirements. Exc...
Acknowledgements Mr. Mohamed Salem and Mr. Patrick Armstrong  (Shimadzu R&D group) developed Canadian  PONA software. Mr...
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Combining Methods CAN/CGSB-3.0 and ASTM D-5580 in a Single GC Platform

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To improve productivity and lower the capital cost, a single gas chromatograph has been configured to perform two standard methods: CAN/CGSB-3.0 and ASTM D-5580.
Detailed hydrocarbon (DHA) analysis of automotive gasoline has become a routine gas chromatographic method. The Canadian standard CAN/CGSB-3.0 requires cryogenic temperature programing to provide better separation of early-eluting components than conventional non-cryogenic DHA measurements. Determination of aromatics in the presence of methanol and ethanol is also an important requirement for bio-ethanol; method ASTM D-5580 is the standard method for this analysis.

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Combining Methods CAN/CGSB-3.0 and ASTM D-5580 in a Single GC Platform

  1. 1. Combining Methods CAN/CGSB-3.0 andASTM D-5580 in a Single GC PlatformZhuangzhi ‘Max’ Wang, PhD, Richard Whitney, PhD, Clifford M.Taylor, Nicole Lock, Laura Chambers, GCMS Product Manager,Shimadzu Scientific Instruments, Columbia, MD, USA, 800-477-1227, www.ssi.shimadzu.com
  2. 2. IntroductionTo improve productivity and lower the capital cost, a single gas chromatograph hasbeen configured to perform two standard methods: CAN/CGSB-3.0 and ASTM D-5580.Detailed hydrocarbon (DHA) analysis of automotive gasoline has become a routine gaschromatographic method. The Canadian standard CAN/CGSB-3.0 requires cryogenictemperature programing to provide better separation of early-eluting components thanconventional non-cryogenic DHA measurements. Determination of aromatics in thepresence of methanol and ethanol is also an important requirement for bio-ethanol;method ASTM D-5580 is the standard method for this analysis.In this work, the two applications have been successfully integrated into one GC. Themethods of three tests – one for CAN/CGSB-3.0 and two for ASTM D-5580, can beswitched smoothly with minimum effort. Automated software control providesseparation of hydrocarbons in groups and reporting of the results for methodCAN/CGSB-3.0. Repeatability (%RSD) of ASTM D-5580 was less than 1.2% foranalysis No. 1, and less than 1.8% for analysis No. 2.This configuration is not limited to motor gasoline analysis though; it can be applied toother finished products such as blend alcohol and other new green energy products.
  3. 3. InstrumentationGC-2010Plus Columns:  20% TCEP, 0.558m X 0.75mm PONA  Rtx-1 30m X 0.53mm X 5µm LN2 Cryo-cooling TCEP Injection Volume: 1 µL Valve box Temp: 80°C APC1 Pressure: 210.0KPa Rtx-1 GCSolution ver. 2.41 PONASolution ver. 2.60
  4. 4. Canadian PONA Method CAN/CGSB-3.0 Objective Separation of hydrocarbons into types Paraffins, Olefins, Naphthene, Aromatics Separation of each type according to carbon number Method Single capillary column separation of all components, followed by grouping with a post-run program - PONA Solution
  5. 5. Canadian PONA Experimental Column: Rtx-1 PONA 100mX0.25mmX0.5µm Sample: Premium Gas Carrier Gas: He, Linear velocity: 25.6cm/sec Split ratio: 270, Gas Saver: On (split ratio 270 to 5 after 5min) Injector temperature: SPL 275˚C Oven Temperature: 0˚C hold 15min, 1˚C/min to 50˚C, 2˚C/min to 130˚C, 4˚C/min to 270˚C Detector: FID 300 ˚C Injection volume: 0.5 µL
  6. 6. Chromatogram uV(x10,000)5.0 Chromatogram4.54.03.53.02.52.01.51.00.50.0-0.5 5.0 10.0 15.0 20.0 25.0 30.0 35.0 40.0 45.0 50.0 55.0 60.0 65.0 70.0 75.0 80.0 85.0 90.0 95.0 100.0 105.0 110.0 115.0 120.0 125.0 130.0 135.0 min 0.5µL injection of premium gas
  7. 7. Manual Chromatogram Quantification All components are identified and classified
  8. 8. Canadian PONA Report Hydrocarbon RetentionSample name Premium Gas Peak Name Type Time % by Mass % by Mole % by VolumeSample ID Premium Gas Isobutane P 8.66 0.09 0.091 0.121Operater Admin 1-Butene X 9.44 0.019 0.018 0.023ID table CanadianPONA Isobutene O 9.48 0.013 0.013 0.016Comments Premium Gas n-Butane A 9.83 0.88 0.889 1.132Sampling date 2/21/2012 trans-2-Butene X 10.3 0.054 0.053 0.064Analysis date 4/6/2011 cis-2-Butene O 11.02 0.062 0.06 0.072Identified peaks [323/367] 3-Methyl-1-butene O 13.15 0.087 0.085 0.1Total area 19776176 Isopentane O 14.71 5.616 5.636 6.72 1-Pentene P 16.34 0.262 0.256 0.295 Hydrocarbon Type % by Mass % by Mole % by Volume 2-Methyl-1-butene O 17.17 0.451 0.44 0.5Paraffins 3.81 3.80 4.46 n-Pentane P 17.68 1.337 1.342 1.585Isoparaffins 39.31 39.49 42.53 trans-2-Pentene P 18.78 1.042 1.017 1.161Olefins 11.37 11.66 12.14 cis-2-Pentene O 19.79 0.495 0.483 0.544Naphthenes 4.97 5.09 4.79 2-Methyl-2-butene N 20.44 1.267 1.236 1.379Aromatics 29.53 31.95 25.11 "2,2-Dimethylbutane" O 22.51 0.406 0.405 0.461Oxygenates 11.02 8.01 10.99 Cyclopentene O 25.07 0.205 0.195 0.186 4-Methyl-1-pentene O 26.24 0.038 0.038 0.042Density(15deg) 0.75 g/cm3 3-Methyl-1-pentene O 26.32 0.069 0.067 0.074Average molecular Cyclopentane P 26.85 0.254 0.248 0.247weight 99.34 "2,3-Dimethylbutane" O 27.58 1.397 1.395 1.561Reseach Octane Number 89.79Vapor Methyl-tert-butylether O 27.98 7.979 10.963 10.937pressure(37.78deg) 41.56 kPa "2,3-Dimethyl-1-butene" P 28.45 0.031 0.03 0.033 2-Methylpentane P 28.63 2.516 2.513 2.846 trans-4-Methyl-2-pentene P 29.08 0.133 0.13 0.144 3-Methylpentane X 31.17 1.546 1.543 1.719 2-Methyl-1-pentene A 32.33 0.194 0.19 0.206 1-Hexene X 32.55 0.087 0.085 0.094
  9. 9. ASTM D5580-02Scope:Determination of benzene, toluene, ethylbenzene,xylenes, C9 and heavier aromatics, and totalaromaticsSample:Finished motor gasoline
  10. 10. Two Step AnalysisNo.1Determination of benzene and toluene, with 2-Hexanone as internal standard; backflush C8+aromatics and hydrocarbonsNo.2Determination of ethylbenzene, xylenes, and C9+aromatics, with 2-Hexanone as internal standard
  11. 11. ASTM D-5580 Experimental  INJ Temp: 200 °C, Carrier Gas: He, Flow Control Mode: Pressure, INJ Pressure: 160KPa, TCEP Column Flow: 10 mL/min, Rtx-1 column flow: 10 mL/min, Split vent flow: 100 mL/min, Purge Flow: 1mL/min, Split Ratio: 11:1  Valve Box Temp: 80.0°C  Oven1 Temp: 40.0 °C hold 6 min, 2 °C /min to 80 °C, 3 °C/min to 115 °C hold 2.33 min  FID Temp: 250 °C, Makeup Gas: He, Makeup Flow: 20.0mL/min, H2 Flow: 40.0mL/min, Air Flow: 400.0mL/min.  TCD Temp: 200 °C, Makeup Gas: He, Makeup Flow: 8 mL/min, Current: 60 mA  T1: 1.8 min, T2: 6.2 min, T3: 21.0 min, T4: 30.0 min
  12. 12. TCD Chromatogram uV(x10,000) Chromatogram1.21.1 Benzene1.00.9 Ethylbenzene0.80.7 o-Xylene Toluene0.6 2-Hexanone0.50.40.30.2 T1 T20.10.0-0.1 0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0 11.0 12.0 13.0 14.0 15.0 16.0 17.0 18.0 19.0 min
  13. 13. Analysis No.1 uV(x1,000,000) 2-Hexanone Toluene Chromatogram3.00 Backflush Peak2.75 C8+ aromatics and hydrocarbons2.502.252.001.751.501.251.00 Benzene0.750.500.250.00-0.25 2.5 5.0 7.5 10.0 12.5 15.0 17.5 20.0 22.5 25.0 27.5 30.0 32.5 35.0 37.5 min
  14. 14. Calibration Curves: Benzene & Toluene
  15. 15. Premium Gas Analysis No.1 uV(x10,000,000) %RSD < 1.2%1.21.11.0 (n=8)0.90.80.70.60.50.40.30.20.10.0-0.1 0.0 2.5 5.0 7.5 10.0 12.5 15.0 17.5 20.0 22.5 25.0 27.5 30.0 32.5 35.0 37.5 min
  16. 16. Analysis No.2 uV(x1,000,000) Chromatogram 1,2,4-Trimethylbenzene6.05.55.04.54.0 o-Xylene3.5 2-Hexanone Ethylbenzene3.02.52.01.51.00.50.0-0.5 2.5 5.0 7.5 10.0 12.5 15.0 17.5 20.0 22.5 25.0 27.5 30.0 32.5 35.0 37.5 min
  17. 17. Calibration Curves Ethylbenzene, o-Xylene, and1,2,4-Trimethylbenzene
  18. 18. Premium Gas Analysis No.2 uV(x1,000,000) Chromatogram6.05.5 %RSD < 1.8%5.0 (n=8)4.54.03.53.02.52.01.51.00.50.0-0.5 2.5 5.0 7.5 10.0 12.5 15.0 17.5 20.0 22.5 25.0 27.5 30.0 32.5 35.0 37.5 min
  19. 19. Conclusions Mechanical valve-based multidimensional GC-2010 Plus has successfully achieved ASTM D5580 requirements. Excellent retention time stability allows for the ease of determining backflush times. Excellent qualitative and quantitative results. In addition to ASTM D-5580 method, a separate analytical line has been incorporated to be able to run Canadian PONA analysis on the same GC, which has lowered instrumentation cost and improved productivity.
  20. 20. Acknowledgements Mr. Mohamed Salem and Mr. Patrick Armstrong (Shimadzu R&D group) developed Canadian PONA software. Mr. Inoye Tataaki and Mr. Ryosuke Kamae (Shimadzu Japan) developed and supported PONASolution software.

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